Wevj 12 00077

Article
Impact of Relaxation Time on Electrochemical Impedance

Spectroscopy Characterization of the Most Common Lithium
Battery Technologies—Experimental Study and
Chemistry-Neutral Modeling
Md Sazzad Hosen * , Rahul Gopalakrishnan , Theodoros Kalogiannis, Joris Jaguemont , Joeri Van Mierlo
and Maitane Berecibar
MOBI Research Group, Department of Electrical and Energy Technology, Vrije Universiteit Brussel, Pleinlaan 2,
1050 Brussels, Belgium; rahul.gopalakrishnan@vub.be (R.G.); Theodoros.Kalogiannis@vub.be (T.K.);
Joris.Jaguemont@vub.be (J.J.); joeri.van.mierlo@vub.be (J.V.M.); Maitane.Berecibar@vub.be (M.B.)
* Correspondence: md.sazzad.hosen@vub.be
Abstract: In electrified vehicle applications, understanding the battery characteristics is of great

importance as it is the state-of-art principal energy source. The key battery parameters can be identi-
fied by one of the robust and nondestructive characterization techniques, such as electrochemical
impedance spectroscopy (EIS). However, relaxing the battery cell before performing the EIS method

is crucial for the characterization results to be standardized. In this study, the three most common
and commercially available lithium-ion technologies (NMC/graphite, LFP/graphite, NCA/LTO)
Citation: Hosen, M.S.;
are investigated at 15–45 ◦ C temperature, in the range of 20–80% state of charge (SoC) and in fresh
Gopalakrishnan, R.; Kalogiannis, T.;
and aged state of health (SoH) conditions. The analysis shows that the duration of the relaxation
Jaguemont, J.; Van Mierlo, J.;
Berecibar, M. Impact of Relaxation
time before impedance measurement has an impact on the battery’s nonlinear behavior. A rest time
Time on Electrochemical Impedance of 2 h can be proposed, irrespective of battery health condition, considering neutral technology-
Spectroscopy Characterization of the based impedance measurement. An impedance growth in ohmic and charge transfer characteristics
Most Common Lithium Battery was found, due to aging, and the effect of rest periods was also analyzed from an electrochemical
Technologies—Experimental Study standpoint. This experimental data was fitted to develop an empirical model, which can predict the
and Chemistry-Neutral Modeling. nonlinear dynamics of lithium technologies with a 4–8% relative error for longer rest time.
World Electr. Veh. J. 2021, 12, 77.
https://doi.org/10.3390/wevj12020077 Keywords: EIS study; relaxation behavior; impedance growth; aging; chemistry-neutral modeling
Academic Editor: Carlo Villante
Received: 20 April 2021

1. Introduction
Accepted: 13 May 2021
Published: 17 May 2021
Lithium-ion batteries (LiBs) as the preferred energy storage system are becoming
more popular in stationary, transport, and consumer electronics products. Now, globally,
Publisher’s Note: MDPI stays neutral
the highest number of projects are running on electrochemical storage with more than
with regard to jurisdictional claims in
3 GW of installed capacity [1]. Besides, Navigant expects around 14 GW grid-scale battery
published maps and institutional affil- capacity by 2023 among which Li-ion has the largest share [2]. However, different lithium
iations. chemistries are still facing key constraints in terms of performance, cost, and reliability
to expand the application range in both stationary and transport applications. Thus, the
understanding of battery behavior is of great importance to improve battery performance
and its continuous development. Electrochemical impedance spectroscopy (EIS) is an
Copyright: © 2021 by the authors.
elegant nondestructive technology with which to characterize LiBs and a wide variety of
Licensee MDPI, Basel, Switzerland.
electrochemical systems [3].
This article is an open access article
Lithium-based batteries are a classic example of electrochemical systems that follow
distributed under the terms and rocking chair methodology during the charge and discharge process [3]. EIS has been
conditions of the Creative Commons regularly used for lithium batteries on a multiscale level from material characterization [4]
Attribution (CC BY) license (https:// to battery cell aging [5–8] and multilevel from half-cell electrode [9–11] to battery full cell
creativecommons.org/licenses/by/ state of function estimations, i.e., state of charge (SoC), state of health (SoH) [12,13] and
4.0/). battery modeling [14,15]. The impedance measurement has a direct output on battery
World Electr. Veh. J. 2021, 12, 77. https://doi.org/10.3390/wevj12020077 https://www.mdpi.com/journal/wevj

World Electr. Veh. J. 2021, 12, 77 2 of 19
power capabilities which is a key performance-limiting factor in automotive applica-

tions [16,17]. The lithium intercalation/de-intercalation phenomena inside a battery cell
during charge/discharge is a complicated electrochemical process that defines the power
output by considering key factors such as electrolyte conductivity, solid electrolyte interface
(SEI) growth, charge transfer between electrolyte and electrode, etc., [18]. EIS can provide
insight into all these internal affairs separately by excitation through current/voltage signal
amplitude on the frequency domain [19]. The frequency spectrum can be analyzed by
simulating it with simple equivalent circuit models (ECM) which is a common approach
for extracting the battery impedance contributions. The level of complexity may vary by
choosing many circuit elements and cell constructions.
Moreover, regardless of parameter extraction, estimation/modeling (SoC, SoH) or
aging (capacity, impedance fade), very little effort has been made to consider the relax-
ation impact on impedance measurements. EIS is quite a sensitive tool, and the applied
voltage amplitude could receive a misleading spectrum if the cell is not in the equilibrium
state. Besides, cell aging, ambient temperature, and SoC are other considerable parame-
ters on relaxation duration that result in the different voltage plateaus affecting battery
impedance directly [19]. When the current load is terminated then the double-layer ca-
pacitance, concentration gradients disturbance, and SoC local equalization occur, along
with the withdrawal of the polarization effect [20]. These effects are also dependent on the
battery state functions and ambient parameters, along with the different characteristics
of commercially available lithium technologies. Researchers have investigated the effects
of current load interruption from minutes to hours before impedance spectroscopy (IS)
to reach equilibrium states, irrespective of battery condition [12,13] [21–25]. However, no
clear explanation is given to standardizing the rest period and its impact on measurement
output. Barai et al. [26] investigated different types of cell impedance results at fixed SoC
and temperature by neglecting the ohmic resistance change due to a lack of operational
involvement. Based on their experiments, a 4 h rest time is suggested so that the resistances
and capacitance fall within the range of experimental error. Frank et al. [22] improved
the consideration by considering a wider range of temperatures and SoCs and proposed
a mind model. Still, the impact of aging on impedance parameters is neglected which
seriously downgrades battery performance over time as ohmic resistance growth takes con-
trol [6]. In [27], the authors considered IS on detailed SoC range and temperature, including
different aging states, to show the experimental results. However, the rest period effect was
analyzed again at certain SoC and temperatures, not explaining the effect corresponding
to the electrochemical perspective. In this research work, the authors have tried to fill the
gaps in the literature. The novelty of the work can be stated below.
• Both high energy and high-power battery chemistries are considered along with the
different aging (pristine and aged) states. To the best of the authors’ knowledge, such
studies on the most common technologies have not been performed before. Moreover,
investigation of aged cells is also a rare study that has been included in this work.
All the batteries that are aged, used similar cycling conditions for more than 2 years.
Impedance measurements are done following an in-house developed methodology
for another 6 months.
• Variable (low to high) temperatures and SoC ranges are considered for the study of
the impedance change, covering a wide range of experimental conditions.
• From no relaxation to ten different rest periods (up to 5 h) are employed.
• The relaxation impact on the ohmic impedance is modeled and a standard technology-
neutral rest time is proposed that is a unique approach to avoid individual technology-
specific study.
Hence, the study would draw attention to the research community working in bat-
tery material characterization, energy storage device characterization that can improve
the material development process, impedance characterization technique, and fitting
modeling methods.
In the next sections of this paper, impedance spectroscopy theory is briefly discussed
in Section 2, referring to the rest time impact. The cells aging history, IS experimental
setup, and methodology is explained in Section 3 with the necessary published materials.
Section 4 includes extracted battery parameters from the frequency spectrum and relaxation
effect analysis from the perspective of electrochemical phenomena. Finally, Section 5
validates the investigation with the empirical fitting results and in Section 6, key findings
and prospective future work are outlined.
2. Electrochemical Impedance Spectroscopy

2.1. Battery Impedance (Theory)
Li-ion cells are characterized at the beginning of life (BoL) with a certain open circuit
voltage behavior, capacity during charge and discharge, and impedance, which define the
performance in terms of energy and power at a certain temperature and C-rate. These
characteristics are highly affected by aging (calendar/cycling), temperature, and loading
profiles (charging/discharging) which can deviate significantly from the nominal values.
The internal impedance of the Li-ion cells is defined as the opposition to the current
flow, arising from the material composition and their interactions. It is categorized as
ionic, the electrical and interfacial resistances which, respectively, arise from the electrolyte
conductivity, the ion mobility, and the area of the electrodes, then the resistivity of the active
materials, the current collectors, the tabs, the electrolyte, and their interaction, between
the electrolyte and the electrodes to the current collectors and the conductive additives.
Electrical resistance occurs quite fast at a current passage and can be seen in the range of
kHz, whereas ionic and interfacial occur more slowly, typically in the range of a hundred
to mHz.
This total impedance is responsible for driving the operating terminal voltage of the
battery cells away from the open circuit voltage (OCV), by generating overpotentials at
fast and slow instances. As for the former, ohmic resistance within the electrolyte, the
electrodes, tabs, and their interfaces, varies with the material properties and is responsible
for the fast overpotential in the range of milliseconds and it is not dependent on the
current rate or the relaxation time. The charge transfer resistance within the medium is
also generated and at the same time, a double-layer capacitance will be created at the solid
and the liquid interface. With certain anode materials, the SEI formation will contribute
to a certain resistance value. On the other hand, slower time constant phenomena, such
as the concentration polarization, create a diffusion resistance which can be seen in the
liquid and on the electrodes. All these resistances deviate the operating voltage from the
OCV and degrade the performance of the battery cells. These resistances are influenced
by temperature, current (amplitude and duration), and aging, which in turn define the
performance of the cells over their lifetime.
When the current is removed from the battery cells, in the first instance, the ohmic,
the charge transfer, and the discharge of the double-layer capacitor are responsible for the
overpotential, while the diffusion of the ions and their redistribution within the electrolyte
generate the diffusion overpotential until the concentration reaches equilibrium. The effect
of the relaxation time on different time instances on the resistance values will be assessed
in this work by the EIS method.
2.2. EIS Experimental Method

The EIS generates the impedance spectrum over a wide frequency range, typically
from kHz to mHz. The Potentiostat method is applied here as the changes occurring in
the battery energy storage system are not as fast as in other electrochemical systems. The
aforementioned impedance can be seen within this frequency range, at various SoCs and
conditions, as shown in Figure 1.
World Electr. Veh. J. 2021, 12, x FOR PEER REVIEW 4 of 19

aforementioned impedance can be seen within this frequency range, at various SoCs and
conditions, as shown in Figure 1.
Figure1.1.EIS
Figure EISimpedance
impedancespectrum
spectrumofofaaLi-ion
Li-ioncell
cell(reproduced
(reproducedfrom
fromref
ref[28]).
[28]).
Electrical
Electrical(ohmic)
(ohmic)resistance
resistanceisisobtained
obtainedatatthe
theintersection
intersectionofofthe
thereal
realtotothe
theimaginary
imaginary
axis,
axis,whereas
whereasthethesemicircle
semicircleisisassociated
associatedwithwiththe
theSEI,
SEI,the
thedouble-layer
double-layercapacitance,
capacitance,andand
the
thecharge
chargetransfer
transferresistance.
resistance.InInthis
thiscase,
case,the
theSEI
SEIhas
hasaalarger
largerimpact,
impact,another
anothersemicircle
semicircle
will
willbebecreated
createdatathigher
higherfrequencies,
frequencies,which
whichrepresents
representsthe theSEI.
SEI.At
Atthe
thelowest
lowestfrequencies,
frequencies,
usually
usually below 1 mHz, the concentration resistance can be obtained duetotothe
below 1 mHz, the concentration resistance can be obtained due thediffusion
diffusioninin
the
the liquid and the solids. The general form to obtain the impedance at any frequencyis:is:
liquid and the solids. The general form to obtain the impedance at any frequency
EE = |Z|·ejϕjφ= |Z|·(cos ϕ + j sin ϕ)

ŽŽ== I = ǀZǀ ∙ e = ǀZǀ ∙ (cos φ + j sin φ) (1)
(1)
I
Here,ŽŽisisthe
Here, theimpedance
impedancevalue
valueininthe
thefunction
functionofofpotential
potentialEEand
andcurrent
currentI.I.Equation
Equation
(1)isisrepresented
(1) representedasasaacomplex
complexnumber
numberwhere
whereϕφisisthethephase
phasedifference
differencedue
duetotothe
theabsolute
absolute
value
valueofofthetheimpedance
impedance|Z|.
|Z|. Further
Furtheron, on,the
theabsolute
absolutevalue
valuecancanbe
bedivided
dividedintointothe
thereal
real
and
andimaginary
imaginaryparts
partsand
andcreate
createthe
theNyquist
Nyquistplotplotillustrated
illustratedininFigure
Figure1.1.
2.3.
2.3.EIS
EISModeling
Modeling
In
In theliterature,
the literature,different
differentmodeling
modelingmethods
methods[29]
[29]cancanbe
befound
foundwhich
whichinclude
includetheo-
theo-
retical
retical quantitative models (white box), qualitative models with experiments(black
quantitative models (white box), qualitative models with experiments (blackbox),
box),
and
andexperimental
experimental quantitative models. White
quantitative models. Whitebox
boxmodeling
modelingis is more
more related
related to solving
to solving dif-
differential equations,
ferential equations, conducting
conducting temperature,
temperature, andand aging-related
aging-related behavior
behavior to extract
to extract pa-
param-
rameters
eters such such as electrolyte
as electrolyte conductivity,
conductivity, porosity,
porosity, etc. Black-box
etc. Black-box modeling
modeling is basedis based on
on purely
purely mathematical
mathematical models.
models. The models
The models simulatesimulate the electrical
the electrical behavior
behavior withoutwithout any
any infor-
information on the physical properties of the battery. If the correct model is assumed
mation on the physical properties of the battery. If the correct model is assumed with the with
the correct order, the equivalent circuits can be a quantitative model. There is a high proba-
correct order, the equivalent circuits can be a quantitative model. There is a high proba-
bility that the model can be over-or under-modeled. To obtain a model with an optimal
bility that the model can be over-or under-modeled. To obtain a model with an optimal
reproduction of the cell characteristics, the basic structure of a battery must be known. In
reproduction of the cell characteristics, the basic structure of a battery must be known. In
experimental qualitative models, the approach starts from modeling the cell from symmet-
experimental qualitative models, the approach starts from modeling the cell from sym-
ric cells, then half cells, slowly moving towards full cell models. This approach is followed
metric cells, then half cells, slowly moving towards full cell models. This approach is fol-
by different groups, one such example is odd random phase electrochemical impedance
lowed by different groups, one such example is odd random phase electrochemical im-
spectroscopy ORP-EIS [30]. Another approach is to determine the equivalent circuit using
pedance spectroscopy ORP-EIS [30]. Another approach is to determine the equivalent cir-
the DRT or density function of the distribution of relaxation times [31]. This method helps
cuit using the DRT or density function of the distribution of relaxation times [31]. This
in identifying the number of RC circuits in the measured impedance spectrum. In this
method helps in identifying the number of RC circuits in the measured impedance spec-
work, the black box modeling method is used, which has been employed a great deal
trum. In this work, the black box modeling method is used, which has been employed a
in literature. This is quite a popular method while quantifying the aging of lithium-ion
great deal
batteries andindeveloping
literature. EIS-based
This is quite a popular
aging method
models even while
though quantifying
all physical the aging
phenomena areof
lithium-ion batteries and developing EIS-based aging models even
not considered. The advantages of this method are simplicity and reproducibility. though all physical
phenomena
Moreover, are not considered.
several model types The advantages
exist of this
to characterize themethod are impedance
generated simplicity and repro-
spectrum
ducibility.
shown in Figure 1. Typically, the ECM approach is adopted, where electrical parameters
describe the overall impedance. To do so, resistors and either capacitor or constant phase
elements can be used in various topologies based on the Randles’ equivalent circuit [32] to
resemble the electrochemical reactions and the corresponding impedance of the battery
eters describe the overall impedance. To do so, resistors and either capacitor or consta
phase elements can be used in various topologies based on the Randles’ equivalent circ
[32] to resemble the electrochemical reactions and the corresponding impedance of t
battery cells in the frequency domain. In [33], the authors studied LFP power loss by pr
posing a temperature-dependent model with three constant phase element (CPE) paral
branches with a series connected to the Warburg element to capture and analyze the fa
and slow time constants. As stated in [34], the Warburg element is a special case of CP
cells in the frequency domain. In [33], the authors studied LFP power loss by proposing a
when the diffusion angle is seen in the Nyquist plot equals 45°, which is also found in th
temperature-dependent model with three constant phase element (CPE) parallel branches
workwith
andaadopted.
series connected to the Warburg element to capture and analyze the fast and slow
time constants. As stated in [34], the Warburg element is a special case of CPE, when the
3. Experimental is seen in the Nyquist plot equals 45◦ , which is also found in this work
Study
diffusion angle
and adopted.
For this study, the three most common Li-ion technologies were used to identify t
optimal no-load period
3. Experimental Studybefore EIS characterization. All these pouch-shaped cells are ma
ufacturedForbythis
EIGstudy,
and the
commercially available.
three most common Table
Li-ion 1 stateswere
technologies the used
basictobattery
identify specific
tions provided by the manufacturer. On the other hand, Figure 2 shows thecells
the optimal no-load period before EIS characterization. All these pouch-shaped battery p
are manufactured by EIG and commercially available. Table 1 states the basic battery
formance comparison which are the main indicators towards designing a battery pack.
specifications provided by the manufacturer. On the other hand, Figure 2 shows the battery
performance comparison which are the main indicators towards designing a battery pack.
Table 1. Battery cells specifications.
Table 1. Battery cells specifications.
Cell Technology Nominal Capacity Nominal Voltage AC Impedance
Cell Technology
NMC/graphite Nominal Capacity
20 Ah Nominal Voltage
3.65 V AC Impedance
<3mΩ
NCA/LTO
NMC/graphite 5 Ah
20 Ah 3.65 V2.2 V <3 mΩ 0.7 mΩ
NCA/LTO
LFP/graphite 5 Ah
14 Ah 2.2 V3.2 V 0.7 mΩ <5 mΩ
LFP/graphite 14 Ah 3.2 V <5 mΩ
Energy Density
Performance Power Density
Safety Lifespan
Cost
LTO LFP NMC

Figure 2. Comparison of the different investigated cell aspects.
Figure 2. Comparison of the different investigated cell aspects.
All the batteries that were investigated, were aged through lifetime tests, and thus
had different states of health (SoH). The aging conditions were selected carefully to ensure
All the batteries that were investigated, were aged through lifetime tests, and th
result compatibility. Table 2 lists the cycling degradation conditions, such as depth of
had different
dischargestates
(DoD) of health
cycling, (SoH). The
temperature, aging
charge conditions
−discharge were
rates, selected
etc. The carefully
performed aging to ensu
resulttests
compatibility. Table
were part of the 2 lists the
investigation cycling
from degradation
the IWT-BATTLE conditions,
project [35] wheresuch as depth of d
the batteries
chargewere agedcycling,
(DoD) by a moretemperature,
than 2-year long test campaign [36]. The
charge−discharge degradation
rates, trend for these
etc. The performed aging te
aged batteries (Figure 3) was chemistry dependent at 45 ◦ C temperature and performed
were part of the investigation from the IWT-BATTLE project [35] where the batteries we
various full equivalent cycle numbers (FECs). A full equivalent cycle is considered to be
aged the
by aamount
more of than
one 2-year long
full charge test campaign
ampere-hour [36]. The
throughput, baseddegradation
on the nominaltrend for these ag
current.
batteries (Figure 3) was chemistry dependent at 45 °C temperature and performed vario
full equivalent cycle numbers (FECs). A full equivalent cycle is considered to be t
amount of one full charge ampere-hour throughput, based on the nominal current.
Before starting the EIS characterization investigation, all the cells were characteriz
to identify the current battery SoH. The characterization was done at room temperatu
which included two capacity tests with a standard C/3 and C/5 charge−discharge ra
respectively, a pulse power test at different states of charge (SoCs), and a quasi-o
cuit voltage (qOCV) test with C/30 rate. The C-rate refers to the cell datasheet
current value provided by the manufacturer.
World Electr. Veh. J. 2021, 12, 77 Table 2. Cell aging inventory. 6 of 19
Cycling History
Cell
Table No.aging inventory.
2. Cell Charge Discharge C- Performed
DoD Temperature
C-Rate Rate FECs (#)
Cycling History
NMC New
Cell No.
New Cell
Charge Discharge Performed SoH
NMC Aged DoD 90% 45 °CC-Rate
Temperature 0.5C-Rate
C 1 C
FECs (#) 2400 8
LTO
NMC New New New Cell New Cell 100%
LTOAged
NMC Aged 90% 90% 45 ◦ C 45 °C 0.5 C 0.5 C1 C 32400
C 1500
80.76% 7
LTO New New Cell 100%
LFP
LTO New
Aged 90% ◦
45 C 0.5 C New Cell 3C 1500 71.60%
LFP
LFPNew Aged 90% 45 °CNew Cell 0.5 C 1 C 100%
1800 7
LFP Aged 90% 45 C◦ 0.5 C 1C 1800 78.01%
Figure
Figure Capacity
3. 3. degradation
Capacity of agedof
degradation cells
agedunder similar
cells undertestsimilar
conditions.
test conditions.
Before starting the EIS characterization investigation, all the cells were characterized
The the
to identify electrochemical
current battery SoH.impedance spectroscopy
The characterization test aton
was done characterized
room temperature, cells w
which
ducted included two capacity
with Biologic’s tests with device.
MPG-205 a standard TheC/3 can −perform
and C/5 charge
equipment dischargeEISrate,measur
respectively, a pulse power test at different states of charge (SoCs), and
the frequency range from 10 μHz to 20 kHz and each of the eight channels can p a quasi-open circuit
voltage (qOCV) test with C/30 rate. The C-rate refers to the cell datasheet nominal current
maximum of 5 A to charge−discharge the battery cell. All the test temperatures w
value provided by the manufacturer.
suredTheby a controlled
electrochemical temperature
impedance environment
spectroscopy using climate
test on characterized chambers.
cells was conductedFigure
ically
with represents
Biologic’s the measurement
MPG-205 procedure
device. The equipment performed
can perform for more than
EIS measurement 6 months.
in the
frequency range from 10 µHz to 20 kHz and each of the eight channels
pedance tests were done, and the results were processed, using the commercially a can provide a maxi-
mum of 5 A to charge−discharge the battery cell. All the test temperatures were ensured
Biologic’s EC-lab software yielding a fitting error of less than 3% that is consid
by a controlled temperature environment using climate chambers. Figure 4 graphically
ceptable.the measurement procedure performed for more than 6 months. The impedance
represents
Thedone,
tests were variation
and theof the parameters.
results were processed,suchusingas thethe state of health,
commercially availablestate of charge, t
Biologic’s
EC-lab software yielding a fitting error of less than 3% that is considered
ture, relaxation time along with cell chemistry and capacity, were studied to ach acceptable.
purpose of this research. The whole test procedure, which was followed, can be ex
as the following steps.
Step 1. The battery cell was fully charged with a constant-current constant
(CCCV) process with a C/5 rate considering the actual C/5 capacity value of the ce
period of 30 min was imposed to stabilize ion movement.
Step 2. The cell was discharged to specific SoC points (80%, 50%, 20%) takin
capacity into account.
Step 3. Ten different relaxation times ranging from 1 min to 5 h, were ensured after
reaching every SoC before doing a Potentiostatic EIS measurement. The voltage ampli-
tude was kept at 4.3 mV to avoid distortion by imposing an AC signal in the range of 10
kHz to 5 mHz frequency.
Step 4. The measurement was done for three different temperature values of 15 °C,
25 °C, and 45 °C, which correspond to the typical battery operating condition tempera-
tures.
EISmeasurement
Figure4.4.EIS
Figure measurementflowchart
flowchartofofthis
thisresearch.
research.
Thereason
The variation of the parameters.
for choosing such as theand
these temperatures state of health,
three SoCs was statetoofminimize
charge, tempera-
the ag-
ing impact during testing with stressful conditions at high/low temperatures to
ture, relaxation time along with cell chemistry and capacity, were studied andachieve
SoC lev-the
purpose of this research. The whole test procedure, which was followed,
els. The cells were re-tested at 25 °C to check the capacity variation after the completion can be explained
ofastests
the following
at various steps.
temperatures and there was not much difference found in the capacity
Step
values obtained 1. Theatbattery cell wasoffully
the beginning charged
the test with atoconstant-current
compared the final validation constant-voltage
results.
(CCCV) process with a C/5 rate considering the actual C/5 capacity value of the cell. A
4.rest period
Results andof Discussion
30 min was imposed to stabilize ion movement.
Step 2. The cell was discharged to specific SoC points (80%, 50%, 20%) taking actual
4.1. Equivalent
capacity into Circuit
account. Selection and Test Conditions
The
StepNyquist
3. Ten plot for a lithium-ion
different relaxation times battery generally
ranging fromconsists
1 min to of 5two semicircles
h, were ensured which
after
represent the cathode and anode. The anode semicircle is seen
reaching every SoC before doing a Potentiostatic EIS measurement. The voltage amplitude at higher frequencies
whereas
was keptthe at cathode
4.3 mV tosemicircle is seen by
avoid distortion at middle
imposing frequencies.
an AC signal These
in thesemicircles
range of 10arekHzgen-to
erally
5 mHz dependent
frequency.on the charge transfer reactions occurring at the anode and cathode,
considering
Step 4.the Theelectrode
measurementmaterial
was(uniform
done forcoating/mixture, morphology)
three different temperature and of
values 15 ◦ C,
surface
◦
characteristics ◦
25 C, and 45 (potential distribution,
C, which correspond toroughness, etc.) [37].
the typical battery At higher
operating frequencies,
condition an in-
temperatures.
ductive behavior
The reason for is seen, which
choosing is due
these to the connection
temperatures cables
and three SoCsusedwastotoconnect
minimize thethe
cells to
aging
impact
the tester.during testingatwith
In contrast, stressful
the lower conditions
frequencies, oneat can
high/low
observe temperatures
a tail that can and
be SoC levels.
a straight
Theascells
line wellwere
whichre-tested at 25 ◦the
represents C todiffusion
check theprocess
capacity atvariation
the anode after
andthe completion
cathode in theoflith-
tests
at various
ium-ion temperatures
battery. Normallyand an there was not
equivalent much
circuit difference
is chosen found
to fit in the capacity
the impedance values
spectra to
obtained
extract theat the beginning
parameters. Theof the test
circuit compared
is selected to the
based onfinal validation
simplicity withresults.
a better represen-
tation of the internal parameters of the battery and ease to use in battery management
4. Results
systems [38].and
As Discussion
mentioned before, the two semicircles are expected to represent the anode
and cathode, but this is Selection
4.1. Equivalent Circuit not whatand Test Conditions
is observed in commercial cells, the impedances of anode
The Nyquist plot for a lithium-ion battery generally consists of two semicircles which
represent the cathode and anode. The anode semicircle is seen at higher frequencies
whereas the cathode semicircle is seen at middle frequencies. These semicircles are gen-
erally dependent on the charge transfer reactions occurring at the anode and cathode,
considering the electrode material (uniform coating/mixture, morphology) and surface
characteristics (potential distribution, roughness, etc.) [37]. At higher frequencies, an in-
ductive behavior is seen, which is due to the connection cables used to connect the cells
to the tester. In contrast, at the lower frequencies, one can observe a tail that can be a
straight line as well which represents the diffusion process at the anode and cathode in
the lithium-ion battery. Normally an equivalent circuit is chosen to fit the impedance
spectra to extract the parameters. The circuit is selected based on simplicity with a better
representation of the internal parameters of the battery and ease to use in battery manage-
ment systems [38]. As mentioned before, the two semicircles are expected to represent the
anode and cathode, but this is not what is observed in commercial cells, the impedances of
and cathode
anode electrodes
and cathode are notare
electrodes distinguished
not distinguishedclearly. This could
clearly. be attributed
This could to the to
be attributed chem-
the
chemical effects occurring at almost the same time-constants on both the electrodes Only
ical effects occurring at almost the same time-constants on both the electrodes [39]. [39].
one semicircle
Only one semicircleis found in most
is found of theofSoC
in most the levels and temperatures,
SoC levels and temperatures, except at certain
except low-
at certain
temperature conditions
low-temperature conditions when whencoupled withwith
coupled low low
SoC SoClevels. Hence,
levels. the semicircle
Hence, is con-
the semicircle is
sidered to represent
considered to represent the thecharge
chargetransfer processes
transfer processesoccurring
occurringat electrode−electrolyte
at electrode−electrolyte inter-
phase [29].[29].
interphase In both the Randles’
In both the Randles’ circuits in Figure
circuits 5, L15,represents
in Figure L1 represents the inductance
the inductance that
comes
that fromfrom
comes the cables
the cablesand andconnections
connections to theto cell. R0 represents
the cell. R0 representsthe ohmic
the ohmic resistance (R0)
resistance
which
(R0) is theisvalue
which obtained
the value obtainedfromfrom the point where
the point wherethe impedance
the impedance spectra cut the
spectra cut real axis
the real
axis
in thein Nyquist
the Nyquist plotplot
and and it is itthe
is the
onlyonly parameter
parameter thatthatcan can be obtained
be obtained directly
directly from fromthe
the impedance
impedance spectrum.
spectrum. It represents
It represents the the conductivity
conductivity of theof the electrolyte
electrolyte therefore
therefore thethe re-
resistance offeredfor
sistance offered forlithium-ion
lithium-iontransport
transportas as well
well asas the
the intrinsic resistance,
resistance, including
including the the
contact
contact resistance
resistance and and thethe resistance
resistance within
within the the active
active materials
materials [40,41].
[40,41]. R1 R1 (only
(only inin the
the
bottom circuit) represents charge transfer resistance (R ) for the
bottom circuit) represents charge transfer resistance (Rctct) for the processes occurring on processes occurring on
both
both the
the anode
anode and and cathode
cathodeelectrodes,
electrodes,similarly
similarlyititisisaacombination
combinationof ofLi+Li+ dissolution
dissolutionand and
resistance
resistance to the Li+ traveling through the SEI and into the active material, Q1
to the Li+ traveling through the SEI and into the active material, Q1 represents
represents
the
the capacitances
capacitancesof ofthe
the anode
cathode electrodes.
electrodes. The The capacitance
capacitanceis is modeled
modeledthrough
through
aa CPE
CPEwithwithaadispersion
dispersionconstant
constant(the (thesemicircle
semicircleisismodeled
modeled bybya CPE
a CPE as as
its its
center-point
center-point is
not on the X-axis of the impedance spectrum [42]). Q represents
is not on the X-axis of the impedance spectrum [42]). Q represents the Warburg impedance the Warburg impedance
which
which is is the
theimpedance
impedance at atlower
lowerfrequencies
frequenciesrelatedrelatedto tomass
masstransport
transportmodeled
modeledthrough
through
CPE as the slope is not 45 ◦ [43].
CPE as the slope is not 45˚ [43].
Figure 5.
Figure 5. The
The chosen
chosen circuits
circuits for
for modeling
modelingthe
the impedance
impedancebehavior.
behavior.
The
The bottom
bottom circuit
circuit was
was used
used at atlower
lowerSoC
SoClevels
levels(<20%
(<20% SoC)
SoC) at at1515◦°C
C because
becausethere
there
was
wasaa two-semicircle
two-semicircleformation.
formation. A A similar
similar approach
approachof of using
using aa different
differentequivalent
equivalentcircuit
circuit
for
for low-temperature
low-temperatureconditions
conditionshas hasbeen
beenrecorded
recordedin in[9].
[9]. Even
Eventhough
thoughthe theresistances
resistancesand and
capacitances
capacitances werewere split
split (for
(for anode
cathode charge
charge transfer
transfer resistance
resistance processes)
processes) to to
represent both the semicircles, the values were very small; hence when
represent both the semicircles, the values were very small; hence when the parameters the parameters were
plotted, a singlea value
were plotted, singlefor resistance
value and capacitance
for resistance representing
and capacitance both the electrodes
representing was
both the elec-
obtained by summing up the values. In [29] it was proven that one
trodes was obtained by summing up the values. In [29] it was proven that one RC circuit RC circuit was the best
to
wassimulate
the bestcharge transfercharge
to simulate resistances for resistances
transfer different factors, such as factors,
for different state of such
charge,
as state
state of
of
health,
charge,and temperature,
state of health, and andtemperature,
an additionaland RC an
circuit could represent
additional RC circuit thecould
rangerepresent
of diffusionthe
processes. Here in processes.
range of diffusion this research,Here RQincircuits were used
this research, insteadwere
RQ circuits of RCused
circuits.
insteadSuch an
of RC
approach
circuits. Such an approach to fitting has already been mentioned in different worksTo
to fitting has already been mentioned in different works of literature [21,43]. of
fit the spectrum
literature [21,43].using
To fitthethechosen
spectrum circuit, a fitting
using method
the chosen of simplex
circuit, a fittingand randomize
method was
of simplex
applied together.was applied together.
and randomize
Figure
Figure 66 shows
shows an an example
example of ofthe
the observed
observedimpedance
impedance curve curve at atdifferent
differentrelaxation
relaxation
times for the new NMC cell at 15 ◦ C for 50% SoC. From the graph, one can see that
times for the new NMC cell at 15 °C for 50% SoC. From the graph, one can see that the
ohmic resistance (R0) variation with time was minimal and that of charge transfer re-
sistance (Rct) was more significant, comparatively. When two semicircles were obtained at
low temperature/SoC conditions, the values extracted were very small, thus, when the
parameters were plotted, a single value for resistance, and capacitance representing the
the ohmic resistance (R0) variation with time was minimal and that of charge transfer
World Electr. Veh. J. 2021, 12, x FOR PEER REVIEW
resistance 9 of 19
(Rct ) was more significant, comparatively. When two semicircles were obtained
World Electr. Veh. J. 2021, 12, x FOR PEER REVIEW 9 of the
at low temperature/SoC conditions, the values extracted were very small, thus, when 19
parameters were plotted, a single value for resistance, and capacitance representing the
sum of R1 and R2 values.
Figure 6. Nyquist plot for fresh NMC cell at various relaxation times (50% SoC at 15 °C).
Nyquistplot
Figure6.6.Nyquist plotfor
forfresh
freshNMC
NMCcell
cellatatvarious
variousrelaxation
relaxationtimes
times(50%
(50%SoC
SoCatat15 ◦ C).
15°C).
Figure
4.2.
4.2.Impedance
ImpedanceMeasurement
MeasurementofofNMC NMCCellsCells
4.2. Impedance
Figure 7 Measurement
shows the of NMC
extracted Cells of ohmic resistances through the equivalent cir-
values
Figure 7 shows the extracted values of ohmic resistances through the equivalent circuit
cuit
modelFigure
model 7 shows
for
for new new the extracted
and and
aged aged
NMCNMC values
cells cells of ohmic at resistances
respectively
respectively through
at various
various the
temperatures
temperatures andequivalent
andThe
SoCs. cir-
SoCs.
key
cuit
The model
key for new
difference and
found aged NMC
between cells
both respectively
cells was the at various
scale at temperatures
which the
difference found between both cells was the scale at which the resistances were observed and
resistances SoCs.
were
The
for key
newdifference
observed for new
and agedandfound
aged
cells. between
The cells.
new The both
cell new cells
ohmic cellwas theresistances
ohmic
resistances scale
wereatinwhich
were
the the resistances
in of
range the range
1.27 ofwere
to 1.461.27
mΩ
observed
to 1.46 mΩ for atnew and
different aged cells.
conditions The new
(SoC, cell ohmic
temperature, resistances
and were
relaxation in the
time)
at different conditions (SoC, temperature, and relaxation time) whereas, for aged cells, the range of
whereas, 1.27
for
toranges
aged1.46 mΩ
cells, at3.03
the
were different
ranges conditions
were
to 3.9 mΩ. (SoC,
3.03 to 3.9 mΩ.temperature, and relaxation time) whereas, for
aged cells, the ranges were 3.03 to 3.9 mΩ.
Figure
Figure7.7.Ohmic
Ohmicresistances
resistancesfor
fornew
new(left)
(left)and
andaged
aged(right)
(right)NMC
NMCcells.
cells.
Figure 7. Ohmic resistances for new (left) and aged (right) NMC cells.
Therefore,this
Therefore, thisisisa aclear
clearindication
indicationthatthatthe
theelectrolyte
electrolytehashasdegraded
degraded(loss
(lossofofconduc-
conduc-
tivity)
tivity) ininthe
theaged
Therefore, aged cells,
thiscells, which
is a clear
which isisthe
thekey
indication key
thatcontributor ofofimpedance
the electrolyte
contributor impedance
has degradedincrease while
(losswhile
increase aging
of conduc-
aging
towards
tivity)
towards inthetheend
the endof
aged ofcells,
life (EoL)
life (EoL)
which[11].
is the key were
There no
no indications
contributor of
ofother
of impedance
indications parasitic
increase
other reactions
while
parasitic agingas
reactions
asthe
theevolution
towards the end
evolution of resistances
ofof life (EoL) with
resistances [11]. an
with increase
There
an were in relaxation
norelaxation
indications time
time showed
of showed
other goodagreement
parasitic
good agreement
reactions
as theno
with evolution
significantof resistances
increase orwith an increase
decrease in valuesin relaxation
[44]. Lowertime showed good
temperature and agreement
lower SoC
with no to
seemed significant
have highincrease or decrease
resistance in values
values, where [44]. Lower
the reason temperature
for this and lower
behavior could be dueSoC
to
seemed
the to have
increase high
of the resistanceconductivity
electrolyte values, where andtheion
reason for this
kinetics at a behavior could be due
higher temperature to
and
the increase of the electrolyte conductivity and ion kinetics at a
vice versa at a lower temperature [45]. In Figure 7, the grouping was quite narrow for higher temperature and
World Electr. Veh. J. 2021, 12, x FOR PEER REVIEW

with no significant increase or decrease in values [44]. Lower temperature and lower 10 of 19
SoC
seemed to have high resistance values, where the reason for this behavior could be due to
the increase of the electrolyte conductivity and ion kinetics at a higher temperature and
vice versa
different at a lower temperature
temperatures and SoCs whereas [45]. In Figure
it was 7, thefor
spread grouping
the agedwas cell.quite narrow for
The impedance
different temperatures and SoCs whereas it was spread for the aged cell.
values did not evolve after 1 h of relaxation time and stabilized quite well after 2 h of rest The impedance
values
for bothdid
the not evolve
cells. afterthe
Further, 1 hcells’
of relaxation
impedance timedidand
notstabilized
decay or quite
evolvewell
muchafter 2 h 2ofhrest
after of
for both
relaxation. the cells. Further, the cells’ impedance did not decay or evolve much after 2 h
of relaxation.
Figure 8 presents the extracted values of charge transfer resistance (Rct) for new and
Figure
aged cells at 8various
presents the extracted
conditions. The values
Y-axis of of charge transfer
the figures resistance
is not the same(Rinct )both
for new and
figures.
aged cells at various conditions. The Y-axis of the figures is not the same in both figures.
Rct represents the resistance offered to the lithium-ion solvation on the electrodes (anode
Rct represents the resistance offered to the lithium-ion solvation on the electrodes (anode
and cathode) and its migration through the SEI layer on the anode [46–51]. The striking
and cathode) and its migration through the SEI layer on the anode [46–51]. The striking
difference observed between both new and aged cells was the growth scale at which the
difference observed between both new and aged cells was the growth scale at which
resistances increased in impedance values by factors of 2 to 2.5 times, due to aging. The
the resistances increased in impedance values by factors of 2 to 2.5 times, due to aging.
new cell’s charge transfer resistances were in the range of 0.1 to 3.3 mΩ at different condi-
The new cell’s charge transfer resistances were in the range of 0.1 to 3.3 mΩ at different
tions (SoC, temperature, and relaxation time) whereas, for aged cells, the ranges were 0.48
conditions (SoC, temperature, and relaxation time) whereas, for aged cells, the ranges were
to 7.5 mΩ. Therefore, this was an indication that the electrode surface had changed (in
0.48 to 7.5 mΩ. Therefore, this was an indication that the electrode surface had changed
composition or thickness) which was mostly attributed to the SEI layer increase on the
(in composition or thickness) which was mostly attributed to the SEI layer increase on the
anode and the concentration gradients at the electrode−electrolyte interfaces [52]. There
anode and the concentration gradients at the electrode−electrolyte interfaces [52]. There
was an evolution of resistances with an increase in relaxation time seen in the figure at
was an evolution of resistances with an increase in relaxation time seen in the figure at lower
lower temperatures
temperatures and lowandSoCs.
low SoCs. The values
The values did notdid not evolve
evolve with anwith an increase
increase in relaxa-
in relaxation time
tion
aftertime aftersettle
1 h and 1 h and
down settle
welldown
after 2well after
h rest for 2both
h rest
thefor both
cells the at
except cells except
lower at lower
temperatures
temperatures where thevalues
where the impedance impedance values
were still were stillFurther
increasing. increasing. Further
studies studies
in terms in terms
of increasing
ofrelaxation
increasing relaxation times to more than 5 h are necessary to analyze
times to more than 5 h are necessary to analyze the relaxation phenomenon at the relaxation
phenomenon
lower temperaturesat lower(lower
temperatures
than 15 ◦(lower
C). than 15˚C).
Thecharge
Figure8.8.The
Figure chargetransfer
transferresistances
resistancesfor
fornew
new(left)
(left)and
andaged
aged(right)
(right)NMC
NMCcells.
cells.
Finally,the
Finally, theimpedance
impedancecurves
curvesfor
fornew
newand
andaged
agedNMC
NMCcells
cellsatatdifferent
differenttemperatures
temperatures
and SoCs after 2 h of relaxation are shown in Figure 9 (note the scales). From
and SoCs after 2 h of relaxation are shown in Figure 9 (note the scales). From this compar-this com-
parison, one can observe that the two semicircles in aged cells converged
ison, one can observe that the two semicircles in aged cells converged to one at 20% to one atSoC
20%
SoC with an increase in temperature. One other key aspect is how the values
with an increase in temperature. One other key aspect is how the values or semicirclesor semicircles
camecloser
came closertogether
togetheratathigh
hightemperatures
temperaturesand
andmoved
movedaway
awayatatlower
lowertemperatures
temperatureswhich
which
may refer to the higher and clearer impedance values at 15 ◦ C.
may refer to the higher and clearer impedance values at 15 °C.
World
World Electr.
Electr. Veh.
Veh. J.J. 2021,
2021, 12,
12, 77
x FOR PEER REVIEW 11
11 of
of 19
19
Figure 9. Nyquist plots for new and aged NMC cells at (a) 15 °C, (b) 25 °C, and (c) 45 °C.
Figure 9.
Figure 9. Nyquist
Nyquist plots
plots for
for new
new and
and aged
aged NMC
NMC cells
cells at
at (a) 15 ◦°C,
(a)15 25 ◦°C,
(b) 25
C, (b) 45 ◦°C.
(c) 45
C, and (c) C.
4.3. Impedance Measurement of LTO Cells
4.3. Impedance Measurement of LTO LTO Cells
Cells
The ohmic resistances for new and aged LTO cells are shown in Figure 10. It should
The ohmic
The ohmic resistances
resistances forfor new
new andand aged
aged LTO
LTO cellscells are
are shown
shown in in Figure
Figure 10. 10. It
It should
should
be noted the Y-axis is not the same in both figures. For this specific cell type, R0 values
be the Y-axis
be noted the Y-axis is not the same in both figures. For this specific cell type, R0 values
noted is not the same in both figures. For this specific cell type, R0 values
seemed to increase by increasing SoC but staying in the range of 1.15–1.6 mΩ. At the BoL
seemed
seemed to to increase
increase byby increasing
increasing SoC SoC butbut staying
staying in in the
the range
range of of 1.15–1.6
1.15–1.6 mΩ.mΩ. At At the
the BoL
BoL
stage,
stage, lower
lowerohmic
ohmiccontribution
contributionat 1515°C◦ C
compared to to
other temperatures was found to be
stage, lower ohmic contribution atat15 compared
°C compared other
to other temperatures
temperatures was was found
found to
to be
smaller
be thanthan
smaller the other
the temperatures
other temperatures whichwhichwas surprising
was and may
surprising and require
may furtherfurther
require inves-
smaller than the other temperatures which was surprising and may require further inves-
tigation; however,
investigation; in general,
however, the the
in general, temperature
temperature andand the SoC dependency
dependencywere wereunclear.
tigation; however, in general, the temperature and thethe SoC
SoC dependency were unclear.
unclear.
While
While aging, ohmic resistances showed similar dependency and the values increased by
While aging, ohmic resistances showed similar dependency and the values increased by
aging, ohmic resistances showed similar dependency and the values increased by
aa maximum of 18%. Lower impedance values of LTO cells may have referred to no SEI
a maximum
maximum of of 18%. Lower impedance
18%. Lower impedance values values of of LTO
LTO cells
cells may
may havehave referred
referred to to no
no SEI
SEI
growth
growth on the
the anodesurface
surface [53]which which was
thethe opposite for for the NMC cells,cells, compara-
growth on on theanode
anode surface[53] [53] which was was opposite
the opposite the
for NMC
the NMC comparatively.
cells, compara-
tively. Irrespective
Irrespective of
of the SoH, the SoH, LTO cells supported a rest period of 2 h after which
noisethe
tively. Irrespective of theLTO SoH,cells
LTO supported a rest period
cells supported a restof 2 h after
period of 2which
h afterthe which in
the
noise
the in
ohmic the ohmic
resistance resistance
values values
fluctuated fluctuated
within a within a
considerable considerable
limit. limit.
However, However,
the R0 the
values
noise◦in the ohmic resistance values fluctuated within a considerable limit. However, the
R0
at values at 45 °C kept
withrising
a slowwith a slowwhich
steepness, which may have happened due to
R045 C kept
values rising
at 45 °C kept rising steepness,
with a slow steepness,may havewhich happened
may have due to the excitation
happened due to
the excitation of ion-kinetics at the higher temperature. Hence, the
of ion-kinetics at the higher temperature. Hence, the impact of the relaxation period, in impact of the relaxation
the excitation of ion-kinetics at the higher temperature. Hence, the impact of the relaxation
period,
this case,in needs
this case,
to beneeds to be investigated
investigated further with further
longer with
restlonger
periods. rest periods.
period, in this case, needs to be investigated further with longer rest periods.
Figure 10.
Figure Ohmicresistances
10. Ohmic resistances for
for new
new (left)
(left) and
and aged
aged (right)
(right) LTO
LTO cells.
Figure 10. Ohmic resistances for new (left) and aged (right) LTO cells.
Figure 11
Figure 11 (note
(note the
the scales)
scales) compares
compares the
the charge
charge transfer
transfer resistance
resistance (R
(Rctct)) for
for the
the new
new
and Figure
old LTO11cells.
(noteHere,
the scales)
once compares
again, no the charge
clear transferdependency
temperature resistance (Rwas
ct) for the new
observed.
and old LTO cells. Here, once again, no clear temperature dependency was observed. The
and old LTO cells. Here, once again, no clear temperature dependency was observed. The
World
WorldElectr.
Electr.Veh.
Veh.J.J.2021,
2021,12,
12,x77
FOR PEER REVIEW 12
12ofof19
19
plotted curves clearly showed the difference of charge transfer values in terms of SoC,
The plotted curves clearly showed the difference of charge transfer values in terms of
especially at 20% storage SoC. This may have been caused by higher ion-exchange re-
SoC, especially at 20% storage SoC. This may have been caused by higher ion-exchange
sistance in the
resistance reference
in the anode
reference surface
anode [54].
surface The
[54]. Theaged
agedLTO
LTOcells
cellsshowed
showedvarying
varyingcharge
charge
transfer
transfer impedance by rest period which became stable after 2 h of relaxationexcept
impedance by rest period which became stable after 2 h of relaxation exceptthe
the
values
valuesatat45
45°C.
◦ C.The
Theimpedance
impedancevalues
valuesalso
alsoincreased
increasedbybyup
uptoto23%,
23%,compared
comparedtotothe
theBoL
BoL
stage
stagedue
duetotoaging.
aging.
Figure11.
Figure Chargetransfer
11.Charge transferresistance
resistancefor
fornew
new(left)
(left)and
andaged
aged(right)
(right)LTO
LTOcells.
cells.
Finally,the
Finally, theNyquist
Nyquistcurves
curvesfor
fornew
newand
andaged
agedLTO
LTOcells
cellsare
areshown
shownin inFigure
Figure12,
12,based
based
on 2 h of relaxation and at low to high temperatures. In Figure 12, the semicircles
on 2 h of relaxation and at low to high temperatures. In Figure 12, the semicircles were were
squeezed towards the low temperatures especially in the aged samples, meaning
squeezed towards the low temperatures especially in the aged samples, meaning that the that the
EoL charge transfer resistance showed temperature dependency. Both at
EoL charge transfer resistance showed temperature dependency. Both at BoL and EoL,BoL and EoL, the
LTO cells showed no tendency of changing ohmic resistance significantly. In
the LTO cells showed no tendency of changing ohmic resistance significantly. In general,general, the
investigated LTO cells showed higher charge transfer resistance variation towards low SoC
the investigated LTO cells showed higher charge transfer resistance variation towards low
and at low temperature.
SoC and at low temperature.
Figure 12. Nyquist plots for new and aged LTO cells at (a) 15 ◦ C, (b) 25 ◦ C, and (c) 45 ◦ C.
4.4. Impedance Measurement of LFP Cells

Figure 12. Nyquist plots for new and aged LTO cells at (a) 15 °C, (b) 25 °C, and (c) 45 °C.
The new and aged LFP cells’ ohmic resistances are illustrated in Figure 13. It should
be noted
4.4. Impedance the Y-axis is not
that Measurement the same
of LFP Cells in both figures. The values ranged from 2.45 mΩ to
2.85The
mΩnewat BoL, between which at room temperature
and aged LFP cells’ ohmic theillustrated
resistances are impedancesin were found
Figure 13. Itto be the
should
best, comparatively, while for the aged condition, the LFP cell impedances increased in the
be noted that the Y-axis is not the same in both figures. The values ranged from 2.45 mΩ
range of 2.6 mΩ to 3.3 mΩ. Although the ohmic part of the resistances at BoL showed no
World Electr. Veh. J. 2021, 12, 77 to 2.85 mΩ at BoL, between which at room temperature the impedances were found13 toofbe
19
the best, comparatively, while for the aged condition, the LFP cell impedances increased
in the range of 2.6 mΩ to 3.3 mΩ. Although the ohmic part of the resistances at BoL
showed no significant SoC dependency [31], only the temperature influence was clear.
significant SoC dependency [31], only the temperature influence was clear. While at EoL,
While at EoL, R0 values showed SoC influence as well as the temperature effect. By aging,
R0 values showed SoC influence as well as the temperature effect. By aging, the impedance
the impedance values became separated further from each other by SoC and the values
values became separated further from each other by SoC and the values increased at low
increased at lowThis
temperatures. temperatures.
means thatThis means
at low that at low due
temperatures, temperatures,
to electrolyteduedecomposition
to electrolyte
decomposition and SEI growth in the anode graphite surface,
and SEI growth in the anode graphite surface, the ohmic impedance growth the ohmic impedance
develops
growth develops further [33]. In [54], the authors have also elucidated lithium
further [33]. In [54], the authors have also elucidated lithium plating as one of the main plating as
one
agingof the main aging
contributors oncontributors on thethe
the anode, where anode, where
effects werethe effects were
observable observable
compared to thecom-
new
pared
cell. While aging, the R0 values increase by a maximum of 33% for 25 C andfor
to the new cell. While aging, the R0 values increase by a maximum of
◦ 33% 25 °C
11% for
and
15 ◦11% for 15 °C,no
C, however, however, no significant
significant change was change was for
observed observed
45 ◦ C. for 45 °C.investigation
Further Further inves- at
tigation at 45 °Cbetter
45 ◦ C and/or and/or better modeling
modeling methodology
methodology maythe
may verify verify
LFPthe LFP characteristics
characteristics at high
attemperatures.
high temperatures.
New and New andLFP
aged agedcells
LFPshow
cells steady
show steady
ohmicohmic resistance
resistance irrespective
irrespective of the
ofrelaxation
the relaxation
period.period. However,
However, a period
a 2 h rest 2 h restcould
period could be considered,
be considered, as sustainableas sustainable
impedance
impedance
growth could growth could beafter
be observed observed
that. after that.
Figure13.
Figure Ohmicresistances
13.Ohmic resistancesfor
fornew
new(left)
(left)and
andaged
aged(right)
(right)LFP
LFPcells.
cells.
Thecharge
The chargetransfer
transferresistance
resistance (R
(Rctct))isisshown
shownininFigure
Figure1414(note
(notethe
thescales)
scales)forfornew
newandand
aged LFP cells. The cells show SoC dependency at BoL charge transfer
aged LFP cells. The cells show SoC dependency at BoL charge transfer resistance, while resistance, while
duringaging,
during aging,SoC
SoCdependency
dependencybecomesbecomesclearer.clearer.AtAtboth
bothBoL
BoLandandEoL,
EoL,high-temperature
high-temperature
impedances were lower referring to higher kinetics in Li-ion transfer at 45 ◦ C. Charge
45 °C.
impedances were lower referring to higher kinetics in Li-ion transfer at Charge
transferresistances
transfer resistancesincreased
increasedby bydecreasing
decreasingtemperature
temperatureand anddecreasing
decreasingSoC,
SoC,which
whichwaswas
very similar to the NMC cells, proving that the graphite anode was
very similar to the NMC cells, proving that the graphite anode was the key contributor. the key contributor.
SEIgrowth
SEI growthon onthe
theanode
anodesurface
surfaceduring
duringaging agingmaymayhavehavefurther
furtherincreased
increasedthetheimpedance
impedance
values which were in the range of 0.33 mΩ to 5 mΩ. The relaxation
values which were in the range of 0.33 mΩ to 5 mΩ. The relaxation in impedance meas- in impedance mea-
surement showed no significant influence on the R measurement,
urement showed no significant influence on the Rctctmeasurement, irrespective of SoH, irrespective of SoH,
however,aa22hhrest
however, resttime
timeshould
shouldbe beconsidered
consideredagain againas asthe
theoptimal
optimalperiod
periodwhere
whereaastable
stable
impedance value can be expected.
impedance value can be expected.
World
World Electr. Veh. J. 2021, 12, x77FOR PEER REVIEW 14
14 of
of 19
19
Figure 14. Charge transfer resistance for new (left) and aged (right) LFP cells.
Figure 14.
Figure Charge transfer
14. Charge transfer resistance
resistance for
for new
new (left)
(left) and
and aged
aged (right)
(right) LFP
LFP cells.
cells.
The temperature-dependent
Thetemperature-dependent
temperature-dependentNyquistNyquist plots
Nyquistplots
plotswith
witha 2 h rest period are are
depicted in Fig-
The with a 2ah2rest
h rest period
period depicted
are depicted in
in Fig-
ure 15
Figure where
15 the
where curves
the curves showed
showed similar
similarbehavior
behavior atathigh
high temperatures
temperatures and
and were
were ex-
ex-
ure 15 where the curves showed similar behavior at high temperatures and were ex-
panded by
panded by decreasing
decreasing temperature.
temperature. AtAt lower
lower temperatures,
temperatures, two two semicircles
semicircles could
could be
be seen
seen
panded by decreasing temperature. At lower temperatures, two semicircles could be seen
but they remained
but they remained very
very close
close to
to each
each other,
other, both
both for
for new
new and
and aged
aged cells.
cells. The
The separated
separated
but they remained very close to each other, both for new and aged cells. The separated
semicircles in LFP
semicircles in LFP atat low
low temperature
temperature maymay refer
refer to
to the
the additional
additional processes
processes happening
happening in in
semicircles in LFP at low temperature may refer to the additional processes happening in
the LFP,
LFP, which
which is
is considered
considered byby selecting
selecting two
twoRQRQcircuits
circuitsin
inmodeling.
modeling.
the LFP, which is considered by selecting two RQ circuits in modeling.
◦ C, (b) 25 ◦ C, and (c) 45 ◦ C.

Figure 15. Nyquist
Figure 15. Nyquist plots
plots for
for new
new and
and aged
aged LFP
LFP cells
cells at
at (a)
(a) 15
15 °C, (b) 25 °C, and (c) 45 °C.
Figure 15. Nyquist plots for new and aged LFP cells at (a) 15 °C, (b) 25 °C, and (c) 45 °C.
5. Model
5. Model Development
Development and and Validation
Validation
5. Model
5.1. FittingDevelopment
Polynomial Modeland Validation
5.1. Fitting Polynomial Model
5.1. Fitting Polynomial
To predict Model
the impedance for different relaxation times, a simple fitting model was
To predict the impedance for different relaxation times, a simple fitting model was
developed in this
To predict research.
the impedanceFor this, the ohmicrelaxation
for different resistancetimes,
of the investigated cell model
a simple fitting chemistries
was
developed in this research. For this, the ohmic resistance of the investigated cell chemis-
at room temperature was fitted with a second-order polynomial equation
developed in this research. For this, the ohmic resistance of the investigated cell chemis- using Matlab
tries at room temperature was fitted with a second-order polynomial equation using
Curve
tries at Fitting Toolbox. Thewas
room temperature reason behind
fitted with selecting ohmic contribution
a second-order was due to
polynomial equation the
using
Matlab Curve
clear impedance Fitting Toolbox.
growth during The reason
aging, behind
while fittingselecting
the chargeohmic contribution
transfer was
resistance due
Matlab Curve Fitting Toolbox. The reason behind selecting ohmic contribution waswas
duea
to the clear task,
challenging impedance growth
considering during
theduring
different aging, while
battery fitting the charge
technologies transfer resistance
to the clear impedance growth aging, while fitting theand temperature-dependent
charge transfer resistance
was a challenging
ambiguous task,
values.task, considering
The equations can the different
bedifferent
expressed battery technologies and temperature-
as follows.
was a challenging considering the battery technologies and temperature-
dependent ambiguous values. The equations can be expressed as follows.
dependent ambiguous values. The equations can be expressed as follows.
Ohmic resistance, R0 (t, SoC) = a × t2 +2 b × t + g × (SoC) (2)
Ohmic resistance, R0 (t, SoC) = a × t2 + b × t + g × (SoC) (2)
Ohmic resistance, R0 (t, SoC) = a × t + b × t + g × (SoC) (2)
In Equation (2), t is the relaxation time; a, b and g are the fixed coefficients recorded
in Table 3 for low, medium, and high SoC. The proposed fitted empirical model would be
able to estimate the ohmic resistance for different rest times before performing EIS charac-
terization. Unfortunately, no clear trend of the charge transfer resistances at different SoC
was found due to the random distribution of the values of different lithium technologies.
Table 3. Fitting coefficient of Equation (2).

NMC LTO LFP
Fitting Equation
a b g a b g a b g
R0 (80% SoC) = a1 × t2 + b1 × t + g1 × 0.8 −1.5 × 10−7 4.5 × 10−6 1.8 × 10−3 1.0 × 10−8 4.0 × 10−6 2.0 × 10−3 1.5 × 10−6 −3.0 × 10−5 3.1 × 10−3
R0 (50% SoC) = a2 × t2 + b2 × t + g2 × 0.5 3.0 × 10−8 2.0 × 10−6 2.8 × 10−3 −2.0 × 10−7 4.0 × 10−6 3.2 × 10−3 −2.0 × 10−6 3.0 × 10−5 5.0 × 10−3
R0 (20% SoC) = a3 × t2 + b3 × t + g3 × 0.2 −1.2 × 10−7 4.0 × 10−6 7.0 × 10−3 −2.0 × 10−7 1.0 × 10−5 8.0 × 10−3 9.0 × 10−7 −9.0 × 10−6 1.4 × 10−2
5.2. Validation
To validate the model, the same three new (partially aged due to calendar) Li-ion cells
belong to each cell technology, were characterized at 25 ◦ C with short to longer rest periods
before impedance spectroscopy in the range of 1 to 20 h. The same test procedure was
followed, as explained in Section 3. The extracted ohmic contributions modeled by a single
RQ circuit showed in Figure 5, were then compared with a simple empirical fitting model.
The EIS measurement considering short to longer rest times shown in Figure 16 had a
good agreement with the model output. When compared, NMC showed the best-fitted
results with a maximum of 4% relative error to the measured impedance. LTO and LFP
results had a moderate fit with 6% and 8% relative error, respectively. The higher fitting
error for LTO and LFP technologies may refer to the selection of fitting equations in this case.
Further improvement can be achieved if the nonlinearity of distorted data can be modeled
in these two technologies. Modeling of the charge transfer contribution and validation with
longer rest periods at different temperatures would also make the model robust, reducing
the limitations. However, this model can be used to identify the rest period impact on the
impedance change for the studied lithium batteries at room temperature and can be used
as a useful tool to characterize the battery cells of common Lithium technologies.
Figure 16. Validation results of ohmic contributions at (a) 80% SoC, (b) 50% SoC, and (c) 20% SoC.
5.3. Limitations and Potential Study

The research work of investigating the relaxation impact on the most common battery
technologies’ impedance measurement includes a lot of experimental work to cover short
to long rest periods. However, more technologies and a wider range of rest times could
be studied to understand the effect. All the performed experiments do not provide a
complete insight into the understanding of the actual conditions of the electrodes inside
the cell but provide guidance to employ impedance measurement. For such information,
half-cell characterizations through distributed relaxation time (DRT) will help in the precise
interpretation of the impedance spectra which is beyond the scope of this work [55,56] but
could be extended in the next study. Further, this study is only limited to the modeling of
the ohmic impedance, thus, fitting the charge transfer and diffusion contributions could
fulfill the investigation. The measurement sensitivity of commercial cells of other types is
another topic that could be covered.
6. Conclusions
In this study, the variation of cell impedance as a function of the relaxation period
after removing an electrical load was investigated for NMC, LTO, and LFP Li-ion technolo-
gies. The EIS characterization was performed on these commercial cells at new and aged
conditions, at different temperatures, and SoCs with varieties of relaxation periods. It has
been observed that the pure ohmic resistance change with different relaxation times was
not significant, irrespective of the cells’ SoH. However, a clear dependency of impedance
parameters on temperature and SoC was found. While aging, NMC experienced the high-
est impedance growth and LTO, the least. The main reason for this could be attributed to
electrolyte degradation in aged cells and the SEI layer increase on the anode [57].
It has also been observed that 2 h relaxation is enough for the cell to stabilize before
performing the EIS, except for the LTO at 45 ◦ C where a longer rest period is foreseen
to obtain a stable measurement. These tests do not provide complete insight towards
understanding the actual conditions of electrodes inside the cell but provide guidance
to employ impedance measurement. For such information, half-cell characterizations
through distributed relaxation time (DRT) will help in the precise interpretation of the
impedance spectra which is beyond the scope of this work [55,56] but could be extended in
the next study.
Finally, the ohmic contribution of the investigated technologies was fitted to develop a
simple empirical model to estimate impedance parameters at different pause times. Valida-
tion results showed that the fitting could provide a good estimation with a maximum of 4%,
6%, and 8% relative error for NMC, LTO, and LFP technologies, respectively. With further
investigation at other temperatures and by optimizing ECM selection, obtained errors can
be minimized. These results can provide a guideline for impedance characterization for
common lithium batteries. Besides, following the battery 2030+ roadmap [58], this model
showcases that a chemistry-neutral approach can be achieved by optimizing the model
functions in the future.
Author Contributions: Conceptualization, methodology, software, validation, formal analysis, in-

vestigation, data curation, writing—original draft preparation, M.S.H.; conceptualization, R.G.;
methodology, data curation, T.K.; writing—review and editing, J.J., J.V.M., and M.B.; supervision,
M.B. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by Vrije Universiteit Brussel.
Data Availability Statement: The data generated in this study cannot be shared.
Acknowledgments: The cells used in this research are acquired from the BATTLE project which was
funded by the Flemish Agency for Innovation by Science and Technology Directorate (IWT130019).
Further, the authors acknowledge ‘Flanders Make’ for their support to the MOBI research group.
Conflicts of Interest: The authors declare no conflict of interest.
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Impact of Relaxation Time on Electrochemical Impedance

Abstract: In electrified vehicle applications, understanding the battery characteristics is of great

Academic Editor: Carlo Villante

Received: 20 April 2021

World Electr. Veh. J. 2021, 12, 77. https://doi.org/10.3390/wevj12020077 https://www.mdpi.com/journal/wevj

power capabilities which is a key performance-limiting factor in automotive applica-

2. Electrochemical Impedance Spectroscopy

2.2. EIS Experimental Method

World Electr. Veh. J. 2021, 12, 77 4 of 19

EE = |Z|·ejϕjφ= |Z|·(cos ϕ + j sin ϕ)

Performance Power Density

LTO LFP NMC

World Electr. Veh. J. 2021, 12, 77 Table 2. Cell aging inventory. 6 of 19

World Electr. Veh. J. 2021, 12, x FOR PEER REVIEW

4.4. Impedance Measurement of LFP Cells

◦ C, (b) 25 ◦ C, and (c) 45 ◦ C.

Table 3. Fitting coefficient of Equation (2).

5.3. Limitations and Potential Study

Author Contributions: Conceptualization, methodology, software, validation, formal analysis, in-

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